Herbicidal dinitro-1,3-phenylenediamine compounds

ABSTRACT

2,4-Dinitro-1,3-phenylenediamine compounds having a trifluoromethyl group on the aromatic ring. The compounds are useful as herbicides.

DINlTRO-l ,S-PI-IENYLENEDIAMINE COMPOUNDS Inventors: Don L. Hunter,Anaheim; William G. Woods, Fullerton; James D. Stone, Whittier, all ofCalif.; Cecil W. LeFevre, Franklin, Idaho United States Borax & ChemicalCorporation, Los Angeles, Calif.

Filed: Jan. 12, 1973 Appl. No.: 323,153

Related US. Application Data Division of Ser. No. 69,487, Sept. 3, 1970,Pat. No. 3,764,623, which is a division of Ser. No. 875,508, Nov. 10,1969, Pat. No. 3,617,252, which is a continuation-in-part of Ser. No.812,307, April 1,

1969, abandoned.

Assignee:

United States Patent 1 [111 3,903,078

Hunter et al. Sept. 2, 1975 1 HERBICIDAL 1m. 01. ..C07D 203/14; C07D205/04;

C07D 207/04; C07D 211/14 [58] Field of Search 260/239 A, 239 B, 239 E,260/293.69, 326.85, 247.5 R, 293.64,

References Cited OTHER PUBLICATIONS Joshi et al., J. Indian Chem. Soc.29, 193 (1952).

Primary ExaminerAlton D. Rollins Assistant Examiner-Mark L. BerchAttorney, Agent, or FirmJarnes R. Thornton 4 Claims, No DrawingsHERBICIDAL DlNlTRO-l,3-PHENYLENEDIAMINE COMPOUNDS I This application isa divisional of our co-pendingapplication Ser. No. 69,487-filedSept, 3,.1970, now. U.S. Pat. No. 3,764,623, which is a divisionof Ser.- No.875,508 filed Nov. .10, 1969, now us. Pat. .No. 3,617,252, which in turnis a continuation-impart of application Ser. No. 812,307 filed Apr. 1,1969., now abandoned. I i

This invention relates tonovel.trifluoromethyldinitro-l,3-phenylenediamine compoundsandtheir useas herbicides. There is provided by thi s ninvention a class of2,4-dinitro-N-substituted-l ,B phenylenediamine compounds having atrifluoromethyl substituent in the 6-position of the aromatic ringhaving outstanding herbicidal activity.

The novel compounds of this invention can be defined by the formulawherein R R R andR are each seleeted'from hydrogen, alkyl, alkenyl, andalkynyl, with the provisio that at least one of said Rs is a hydrocarbongroup. Also, R,-R and/or R,,-R can represent a portion of a cyclic groupsuch as an alkylene chain to form a heterocyclic group containing carbonatoms in addition to the nitrogen atom which is the point of attachmentto the aromatic ring. I

For convenience in naming the compounds, the amino nitrogen adjacent tothe trifluoromethyl group is referred to as N and the amino nitrogenbetween the nitro groups on the ring is referred to as N". Thus, thenitro substituents are in the 2 and '4 position of the aromatic ring andthe trifluoromethyl group is in the 6 position of the aromatic ring. Itwill be noted'from the above definition that either the N or N aminonitrogen must have at least one substituent thereon thereby excludingthe unsubstituted compound having two amino (-NH groups.

Typical examples of the groups represented by R',, R R and R -as definedabove are hydrogen and the lower alkyl, lower alkenyl, and lower alkynylgroups having up to about 6 carbon atoms, including the cyclic analoguesthereof as well as the halo, hydroxy, and lower alkoxy substitutedderivatives thereof. .Represen tative groups are methyl, ethyl,'n-propyl, isopropyl, nbutyl, sec-butyl', n-pentyl, sec-pentyl,n-hexyL'allyl 2- butenyl, 2-butynyl, 3-butynyl, methallyl, 2-pentynyl,Z-hydroxyethyl, Z-bromoethyl, 2-methoxyethyl, 3- ethoxypropyl,2,2-dimethoxyethyl, 2-chloroallyl, 3- chloropropyl, 4-hydroxy-2-butynyl,l-methyl-2- methoxyethyl, 2-bromoallyl, propynyl, I 4.-chloro.-2-butenyl, '4-bromo-l-butenyl, 3-iodo-2-pentenyl; 4- ehloro-Z-butynyl,cyclohexyl, 'cyelopropyl, cy'clobutyl, cyelohexenyl, and thelike. w

Furthermore. R,-R and/or R;,-R can represent a fragment ofa ring ofwhich the amino nitrogen is a part thereof. such as illustrated by thestructure in which Z isan a lkylene group having from about 2 t0 6carbon atoms in the. chain, and optionally other diethylenoxy,diethyleneimino, and hexamethylene groups.

' Apreferred cla ss of compoundsaceording to this invention are those inwhich RJS hydrogen, R and R3 areeaeh selected from'hydro'gen and alkylof l to Scarbon atoms and R}, is alk'ylof l to 5 carbon atoms. Thus,

representative examples of alkyl are methyl, ethyl, npropyl, isopropyl,sec-butyl, sec-pentyl, and the like. Preferably the total number ofcarbon atoms reprsented R, R, l l- R is about 4 to 8 Compounds in whichboth R, and R are hydrogen represent a further preferred'class. v v IRepresentative examples of such preferred compoundsare v N -see-butyl-N,N -dirnethyl-2,4-dinitro-6-tri- 'fluorome thyl-l,3-phenylenediamineN-ethyl-N,N -diethyl 2,4-dinitro 6-trifluoromcthyl-1,3-phenylenediami'ne i. vN'-methyl-N-sec-butyl-2,4-dinitro-6-trifluoi'omethyl-l,3-phenylenediarnine l N ethyl Nsee-butyl-2,4-dinitro-6-trifluoromethyl- 1,3-pheriylenediamirie vN-methyl-N?,N-di n-propyl-2,4-dinitro-6-tri- I fluoromethyl-l,3-phenyle'nediamine N ,N"-di-n propyl-2',4-dinitro- 6-trifluorornethyl-l ,3-

phenylenediamine v I N methylN,N -diethyl-2,4dinitr0-6-trifluoromethyl-l,3-phenylenediarnine fluorom'ethyl-l,3-phenylenediamineN'-sec-pentyl-N",N-dimethyl-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine I i N",N -diet'hyl-2,4-dinitro-6-trifluorornethyll,3- phenyl'enediami ne I I N" 3"-pentyl )-2,4-dinitro-6trifluoromethyl-l ,3-

phenylenediamine I I N"-sec-butyl-2,4-dinitro-6-trifluoromethyl- 1,3:

phenylenediamine 'N-( l-methyl-Z-methoxyethyl 2,4-dinitro-'6-trifluoromethyl-l,3-phenylenediamine The compounds of thisinvention are either crystalline solids or high boiling liquids.Generally they are only slightly soluble in water and are moderatelysoluble in the usual organic solvents such as ethanol, acetone, etherand benzene. The compounds are readily prepared by reaction of one ortwo amines or ammonia with a 2,4-dihalo-3,S-dinitrobenzotrifluorideaccording to the following equation:

x r R in which X is a reactive halogen such as chlorine or bromine and RR R and R, can have the significance previously assigned.

When R and R are the same as R and R that is when the substituted Namino group is the same as the substituted N amino group in theresultant product, the reaction takes place in one step using at leastfour moles of amine for each mole of2,4-dihalo-3,5-dinitrobenzotrifluoride. When R and R. are different fromR and R the reaction requires two steps in which a different amine is'employed in' each step. In the first step about two moles of the amineforming the N group is reacted with about one mole of the 2,4-dihalo-3,5-dinitrobenzotrifluoride. The first halogen atom replaced is thatbetween the nitro groups on the aromatic ring. This step isadvantageously carried out in a nonpolar solvent such as a hydrocarbonin which the amine hydro halide is insoluble and can be removed byfiltration. In the second step about two moles of the amine forming theN group is reacted with the monoaminosubstituted compound to form theunsymmetrically substituted 1,3-phenylenediamine compound. The secondreaction can take place in a scaled reaction vessel, such as a sealedtube or an autoclave, to avoid losses of amine and provide easy controlof the reaction, or at atmospheric pressure in the presence of asolvent, such as an alcohol, in which the amine is highly soluble. 1nthe case of higher boiling amines it is not necessary to use a sealedreaction vessel for the reaction but it is sufficient merely to carry itout in the presence of a suitable solvent.

A reaction temperature in the range of from about to about 100C.preferably is employed to give good yields of the desired product and asatisfactory rate of reaction, both in the case of using a scaledreaction vessel and when the reactants are brought together in thepresence of solvent. Hydrogen halide is formed as a by-product and, inthe presence of excess amine, is converted to the amine hydrohalidewhich can be readily removed by washing with water or by filtrationafter dissolution of the product in a suitable solvent. The desiredproducts can be purified by well known procedures such as byrecrystallization.

The 2,4-dihalo-3,S-dinitrobenzotrifluoride starting materials arereadily prepared by nitration of the 2,4- dihalobenzotrifluoride with amixture of fuming nitric and fuming sulfuric acids at a temperaturebelow about 80C.

The following examples describe preparation of representative compoundsof this invention, but it is to be understood that the invention is notto be limited to the specific examples given.

EXAMPLE 1 N ,N-bis( diethyl-2,4-dinitro-6-trifluoromcthyl-l ,3-phenylenediamine A heavy walled glass reaction tube of about 50 ml.capacity was charged with 5 grams (0.0163 mole) of2,4-dichloro-3,5-dinitrobenzotrifluoride, ml. of eth- 4 anol and 20 ml.of diethylamine. The reaction tube was sealed and heated in a bath at9499C. for 46.5 hours. The cooled reaction tube was then opened and thecontents evaporated to dryness-to give a solid residue. The

residue was extracted with 200 ml. of refluxing diethyl ether and theinsoluble amine hydrochloride was sepa-' rated therefrom by filtration.The ether extract was evaporated to dryness and the residue dissolved in40 ml. of refluxing 95 percent ethanol and 10 ml. of water. Uponcooling, the product crystallized and was isolated by filtration,obtaining the desired product (30% yield) as a crystalline solid,melting at 72.574.5C. After re-- crystallization, the product melts at7475C.

Analysis: Calculated: C, 47.61; H, 5.60; N, 14.81

Found: C, 47.34; H, 5.58; N, 14.64

EXAMPLE ll N',N*-bis( dimethyl )-2,4-dinitro-6-trifluoromethyl- 1 ,3-phenylenediamine This compound was prepared in a similar manner byreaction of 2,4-dichloro-3,5-dinitrobenzotrifluoride with dimethylamine.The crystalline product melts at l25.5126.5C.

Analysis: Calculated: C, 41.00; H, 4.07; N, 17.39 Found: C. 40.91; H,4.01; N, 17.54

EXAMPLE 111 N,N -bis( di-n-propyl )-2,4-dinitro-o-trifluoromethyl-1,3-phenylenediamine This compound was prepared in a similar manner byreaction of 2,4-diehloro-3,S-dinitrobenzotrifluoride withdi-n-propylamine. The product is a high boiling oil.

EXAMPLE IV I N ,N 'di-sec-butyl-2,4-dinitro-o-trifluoromethyl-l ,3-

phenylenediamine To a stirred solution of 5.00 grams (0.0164 mole) of2,4-dichloro-3,S-dinitrobenzotrifluoride in 25 ml. of absolute ethanoland 10 ml. of dioxane was added 5.04 grams (0.069 mole) ofsec-butylamine. The resultant mixture was stirred under reflux for 24hours. The solvent was then removed by evaporation under reducedEXAMPLES V-XlV The following compounds were prepared in a similar mannerby reaction of 2,4-dichloro-3,5-dinitrobenzotrifluoride with thecorresponding amine.

phenylenediamine; m.p. 169-170C. V1 N,N"-diisopropyl-2,4-dinitro-6-trifluoromethyl-l ,3-phenyl-enediamine; m.p.66.567.5C.

EXAMPLE XV N,N-di-n-propyl-3-chloro-2,6-dinitro-4-trifluoromethylanilineA heavy walled glass reaction tube of approximately 50 ml. capacity wascharged with 7.0 grams (0.023 mole) of2.4-dichloro-3,5-dinitrobenzotrifluoride, 4.64 grams (0.0458 mole) ofdi-n-propylamine and 40 ml. of absolute ethanol. The tube was sealed andheated in an oil bath at 9499C. for 98 hours. The cooled reactionmixture was then evaporated to dryness to give an oily residue which wasextracted with boiling diethyl ether. The insoluble di-n-propylaminehydrochloride was removed by filtration and washed with additionalether. The combined ether filtrates were evaporated to give an oilyorange residue which was dissolved in 100 ml. of absolute ethanol anddecolorized with activated charcoal. The ethanol and volatiles wereremoved by evaporation under reduced pressure to give the product (6.77grams) as a viscous reddish oil.

N N"-di-n-propyl-2.4-dinitro-6 trifluoromethyl-1,3- phenylenediamine Aglass reaction tube was charged with 4.0 grams (0.0108 mole) ofN,N-di-n-propyl-3,-chloro2,6-dinitro-4-trifluoromethylanilinc, 5.82grams (0.0237 mole) of 6.95% ethanolic ammonia and 35 ml. of ethanol.

The tube was sealed and heated in an oven at 100C.

for 68 hours. The contents of the tube were cooled and the ethanolremoved by evaporation. Water was added to the solid orange residue todissolve the ammonium chloride and the insoluble product was separatedby filtration. The product was dissolved in refluxing 95 percentethanol. Upon cooling, orange needles and a yellow powder crystallized.The-yellow powder was identified as 2,4 dinitro-o-trifluoromethyl- 1.3-phenylenediamine and was separated from the desired product byfiltration after extraction with boiling hexane. The desired productdissolved in the hexane and was isolated from the filtrate byevaporation of the hexane. The residue was recrystallized from 95percent ethanol to give orange needles. mp. l24l25C.

Analysis: Calculated: N 15.99 Found: N 16.00

EXAMPLE XVI N,N -dirnethylene-N,N-di-n-propyl-2,4-dinitro-6-trifluoromethyl-l ,3-phenylenediamine Asolution of 4 grams (0.0108 mole) ofN,N-di-npropyl-3-chloro-2,6-dinitro-4-trifluoromethylaniline and 0.93grams (0.0216 mole) of ethyleneimine in 50 ml. of absolute ethanol wasstirred overnight at 35C. The solvent was removed by evaporation underreduced pressure to give a residue which was extracted with boilinghexane. The hexane extract was evaporated to drynessand the residuedissolved in absolute ethanol. After deeolorizing with charcoal, theethanol and volatiles were removed by evaporation under reduced pressureto give the product as a viscous amber oil, which was identified by itsproton nuclear magnetic resonance spectrum.

EXAMPLE XVII N -ethyl-N",N-dimethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamineN,N-dimethyl-3-chloro-2,6-dinitro-4-trifluoromethylaniline was reactedwith ethylamine in a sealed tube as described in Example XV togive thedesired product melting at 51.552.5C.

Representative examples of the many other compounds which can beprepared by the above-described general procedures are:

Nethyl-N-sec-butyl-2,4-dinitro-6-trifluoromethyl- 1,3-phenylenediamine;m.p. 92.594C.

N -sec-butyl-N",N -dimethyl-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; oil

N-sec-butyl-N",N-diethyl-2,4-dinitro-6-trifluoromethyll,3-phenylenediamine; oil.

N -methyl-l\l,N-diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; m p.71.573.5C.

N -methyl-N ,l\l-di-n-propyl-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; 48.5-50.5C.

N ,N -di-n-propyl-N",N -dimethyl-2,4dinitro-6-trifluoromethyl-l,3-phenylenediamine; m.p. 39.54().5C.

N'-ethyl-N",N -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; 54-55.5C.

N,N -diethyl-N ,N"-dimethyl-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; 4546C.

N-methyl-N -sec-butyl-2,4-dinitro-6-trifluoromethyll,3-phenylenediamine; m.p. 8 l 83C.

N ,N -dimethylene-N-sec-butyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; m.p. 9293C.

N -propargyl-N.N-di-n-propyl-2,4-dinitro-6-trifluoromethyll,3-phenylenediamine; oil

N-propargyl-N ,N-diethyl-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; oil N,N'diethyl-N-ethyl-2,4-dinitro-6-trifluoromethyl LEI-phenylenediamine; m.p.64.565.5C.

N -propargyl-N -sec-butyl-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; 5354C.

N,N -dimethyl-N,N-di-n-propyl-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; m.p. 58.559.5C.

N .N -dimethyl- N ,N-diethyl-2 ,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; m.p.

N,l l -diethyl-N"-sec-butyl-2.4-dinitro-6trifluoromethyll,3-phenylenediamine; oil

Nethyl-N.N-di-n-propyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine;oil

N,N -dimethylene-N,N"-diethyl-2,4-dinitro 6-trifluoromethyll,3-phenylenediamine; oil

N -propargyl-N,N -dimethyl-2,4-dinitro-6-tri- 'fluoromethyl-l,3-phenylenediamine;

N-( Z-hydroxyethyl )-N-sec-butyl-2,4-dinitro-6-trifluoromethyl-l,S-phenylenediamine; m.p. 57.558.5C.

N"-cyclopentyl-N -methyl-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; 8788.5C.

N-( l-methyl-Z-methoxyethyl )-2,4-dinitro-6-tri fluoromethyl- 1,3-phenylenediamine;

l20.5l2l.5C.

N 2,2-dimethoxyethyl )-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine;

N"-( 3-chloropropyl )-2,4-dinitro-6-trifluoromethyl-LB-phenylenediamine; m.p. 9494.5C.

N"*-(Z-bromoethyl)-2,4-dinitro6-trifluoromethyll,3-phenylenediamine;m.p. l49l 50C.

N,N"-bis(Z-methoxyethyl)-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; 93-94C.

N-cyclopropyl-2,4-dinitro-6-trifluoromethyl l .3-

phenylenediamine; m.p. l80-l8l.5C.

N -methyl-l I-( B-pentyl )-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; 73.574.5C.

N-sec-amyl-2,4-dinitro-6-trifluoromethyll ,3- phenylenediamine; m.p.l05.5l06.5C.

N methyl-N,N"-diethyleneoxy2,4-dinitro-6-trifluoromethyll,3-phenylenediamine; m.p. 2012()3C.

N-methyl-N'-ethyl-2,4-dinitro-6-trifluoromethyl- ,l,3-phenylenediamine;m.p. 8989.5C.

N,N"-diallyl-2,4-dinitro-o-trifluoromethyll ,3-

phenylenediamine; m.p. 7273C.

N-methyl-N,N-pentamethylene-2,4-dinitro-6-trifluoromethyl-l'.3-phenylenediamine;m.p.

N-( 3-pentyl )-2,4-dinitro-6-trifluoromethyl-l ,3-

phenylenediamine; m.p. l l9.5l2().5C.

N-methyl-N -cyclohexyl-2,4-dinitro-6-trifluoromethyl-l,3-phenylenediamine; l27.5"l28.5"C.

N-( 2-chloroallyl )-2.4-dinitro-6-trifluoromethyll ,3-

phenylenediamine; m.p. l (J2l()3C.

N"-sec-butyl-2,4-dinitro-6-trifluoromethyl l ,3- phenylenediamine; m.p.l26.Sl27.5C.

N .N-diethyl-2.4-dinitro-6-trifluoromethyll ,3-

phenylencdiamine; m.p. 9899C.

N ,N -diethyl-2,4-dinitro-6-trifluoromethyll ,3-

phenylenediamine; m.p. 8586C.

N,N '-di-n-propyl-2.4-dinitro-6-trifluoromethyll ,3-

phenylenediaminc; m.p. 75.576.5C.

N -sec-butyl-2,4-dinitro-6-trifluoromethyll .3-

phenylenediamine; m.p. 586()C.

The following example illustrates a typical preparation of the2,4-dihalo-3,5-dinitrobenzotrifluoride intermediates.

EXAMPLE XVlil 2,4-dichloro-3 ,S-dinitrobenzotrifluoride Fuming sulfuricacid (600 ml.) containing 30-33 percent free SO was stirred in atwo-liter, three-necked flask immersed in an ice bath. Fuming percentnitric acid (585 ml.) was added followed by 148.8 grams (0.692 mole) of2,4-dichlorobenzotrifluoride. This stirred slurry then was heated to76C. and held at 76 i lC. for 96 hours. The mixture was cooled and theacid was drained from the crust of crystalline product. Water 1000 ml)was added to the broken up solid and the stirred slurry extracted with500 ml. of toluene. The toluene solution with another 500 ml. of tolueneadded was washed successively with water (500 ml) twice with 500 ml. of5percent sodium bicarbonate solution, and finally with water (500 ml).Removal of the toluene by evaporation at reduced pressure and dryingovernight gave 166.6 grams (79%) of the desired 2,4-dichloro-3,5-dinitrobenzotrifluoride, m.p. 6772 C. Afterrecrystallization from ethanol the material melts at 7475C.

Reference is made to a copending application of Don L. Hunter, Ser. No.832,860 filed June 12, 1969, which describes and claims preparation ofthe 2,4-dihalo-3,5- dinitrobenzotrifluorides.

The compounds of this invention are excellent herbicides and areespecially useful as selective herbicides for controlling weeds in thepresence of desirable crops, especially the grassy weeds such as, forexample, foxtail, water grass, and crabgrass. Many of the compounds ofthis invention may be used in controlling weeds in desirable grassycrops such as corn and rice, as well as the small grains, and also thebroad leaf crops such as cotton and soy beans. Also, many of thepreferred compounds are effective in controlling wild oats whichconstitute a major problem in small grain crops such as wheat andbarley.

Water grass and related weeds are a serious problem in rice and thediscovery of an effective selective herbicide for this problem is asignificant advancement in the art. Such a discovery is surprising andunexpected in view of the phytotoxicity of many other aromatic aminederivatives to grassy crops such as rice. It has also been found thatthe specific phenylenediamines of this invention are much less volatilethan many other substituted aromatic amines and will move better in thesoil, as well as possessing better ultraviolet stability.

The compounds can be applied as both a pre-emergence or a post-emergencetreatment; that is they can be applied to soil in which the weeds willgrow or they can be used to kill or suppress the growth of weeds or tokill or prevent the emergence of seedlings of undesirable plants. Thus,the compounds can be used to control the growth of weeds by applying aphytotoxic amount of one or more of the active compounds of thisinvention to the locus to be protected, that is, soil in which the weedsare growing or will grow or the foliage of the growing plants. -Weeds asused herein is meant to include any plant growth which is undesirable.

Generally an application rate of from about 0.1 to about 25 pounds ofone or more of the active compounds per acre is effective incontrolling. plant growth. Preferably an application rate of from about0.25 to about 5 pounds per acre is employed. At such rates theundesirable weeds are killed or stunted with little or no injury todesirable crops.

9 The following examples illustrate the herbicidal ac tivity of typicalcompounds of this invention.

evaluated and rated as described in Example XIX. The

Y following results were obtained.

EXAMPLE xix TABLE II The compounds to be tested were evaluated as pre- 5Compound A B Cumpound C Plant Specie .Pre Post 7 Pre Post Pre Postemergence herbicides on a broad class of representav tive weeds andcrops. Greenhouse flats were planted to 3 53f g g g 3 pigweed, cheat,wild oats, foxtail, morning-glory, water wild 9mg 3 3 I; 3 I; 5 grass,rice, sugar beets. cotton. corn, barley, and soy- FOXIHFI 9 3 9' 8 9 5 b0 th d f l t. th fl t 7 1O Momiiig-glory U 3 4 4 0 3 eans. e same ay 0 pan ing e a s were water grass 9 8 9 9 9 7 sprayed with an ethanolsolution of the compound to be Rice w 0 0 Y 0 0 0 0 Sugar beets 6 l 9 42 1 tested at a rate of two pounds per acre. The flats were Cmmn O I 6 44 0 3 kept in the greenhouse and watered when needed. c 0 o 4 2 0 0Twenty-one days after treatment, the plants were eval Bmlc) (l l 0 0 l It I I Soybeans 3 3 4 O 3 uated for herbicidal activity and rated on a 0to 9 scale in which 0 =no effect; 5 =substantial injury with slight killand 9 complete kill. The following results were Compound A N, mcthylN3N3 di n prOpyL24 obtained. 1 Y

9 dinitro-6-trifluoromethyl-l ,3-phenylenediamine TABLE I CompoundActivity* (DTP 2.4-dinitro-htrifluoromethyl-L3- P CH WO F M W R SB CO CRB SO phenylenediamine) N-ethyl-N"-sec-butyl- 9 0 s 9 0 9 I 0 4 3 i 0 0DTP N'-methyl-N"-sec-hutyl- 9 l 8 9 l 9 (l 4 l 4 l) l DTP NN-dimeth\-I-N" N- 9 l 2 7 0 9 0 1 0 u o 0 diethyLDTP N'sechutyl-N-XN 9 3 x 9 l 90 i 0 i 1 l dimethyl-DTP N-see-butyl-N" N- 2 o 1 9 o 7 0 u 0 o l nLliethyLDTP N.N-dimethylene-N. 8 l 5 6 4 l l 0 t) 0 N -di-nprnpyl-DTP *Ppigweed M morning .glory CO cotton CH cheat W water grass CR corn WOwild oats R rice B barley F foxtail SB sugar beets S0 soyheans EXAMPLEXX Compound B N*,N"-di-n-propyl-2,4-dinitro-6-tri- 40 fluoromethyl-l3-phenylenediamine The com ounds to be tested were evaluated as both pCompound C N-methyl-N",N"-diethyl-2,4-dinitroa pro-emergence andpost-emergence treatment on a 6 -trifluoromethyll ,3-phenylenediaminebroad class of weeds and crops. Greenhouse flats were planted to thespecies tested in Example XIX and the EXAMPLE XXI l' n in wit anethaflats l n the Same day p t g h Greenhouse flats were planted toplgweed, crabgrass, no] solution of the compound to be tested at a rateof 2 wild oats, giant foxtail, sorghum, water grass, rice, pounds peracre. I

, Johnson grass, cotton, corn, barley, and soybeans. On Another set offlats with the same plants was treated the same day as planting, theflats were sprayed with an after the plants had emerged and were about 1inch in ethanol solution. of the compound to be tested at a rate height.These flats were also sprayed with an ethanol Y Y Y Y of 1 pound peracre. The flats were kept in the greensolution of the compound at a rateof 2 pounds per acre h Y ouse and watered. when needed. Sixteen daysafter in order to determine post-emergence activity. The

treatment the flats were evaluated and the herbicidal flats were kept inthe greenhouse and watered when activity rated as described in ExampleXIX. The follownceded. Twenty-two days after treatment the flats were mgresults were obtained.

TABLE III Compound I y 9 i Aetivity* (DTP 2,4-dinitro-6-trifluuromethyll .3 'P CB WO F S(; W R JG CO CR B, SO phenylenediamine IN'vN'==-dit-ih vi-DTP 4 5 1 3 i 2 0 4 l u u 0 N'.N-tiiull IDTP Y .0 2 12 (i 1 0 2 o (l u u N'.N"-L|i-n-propyl- 5 'l 7 l 3 (J 5 l (l (I l DTPN'eth)'l-N.N -tlicth)l- 5 o 4 x u x o 5 (i o u (I DTP N'-cXh,\lN.N"-tli-H- i 3 5 Q 7 (1 (i (1 5 u o (I o proud- DTP i i v *P pigweetl1 5G sorghum (O cotton ("II crzibgrass W water grass CR corn W() \VllLloats R rice B barley TABLE Ill-continued Compound Activity* (DTP2,4-dinitro-6- trifluoromethyll ,3- P CB WO F SG W R JG CO CR B SOphenylenediamine F foxtail JG Johnson grass S soybean l0 V-continuedGreenhouse flats were planted to soybenas, velvet- Plum Spec? Acnmy Rmmgleaf, oats, and millet. On the same day as planting the g g f 2 e vet eaflats were sprayed with an ethanol solution of the com- Com 0 Cotton 0pound to be tested at a rate of pounds per acre. The flats were kept inthe greenhouse and watered when needed. Nineteen to twenty-one daysafter treatment the flats were examined and the plants rated forherbicidal activity as described in Example XlX. The following resultswere obtained.

TABLE [V Compound Activity* (DTPZ.4-dinitro-6-trifluoromethyl-1,3-phcnylcnediamine) SO VL O Ml N,N-dimethylenc-N-see-butyl- U l 3 9 DTP N,N'-dimethyIenc-N".N-diethyl- 0 0l 9 DTP N'-propargyl-N-scc-butyl-DTP 0 2 3 8 N'-propargyl-N -diethyl-DTP2 3 5 9 N'-propargyl-N.N-di-n-propyll l 6 9 DTPN"-cyclopentyl-N-mcthyl-DTP 0 4 5 9 N-ally|-DTP 2 4 4 9 N-(3-chloropropyl )-DTP 0 4 3 9 N-( Z-ehloroallyl )-DTP 0 3 2 9 N,N"'-bis(2-methoxyethyl )-DTP 4 5 6 9 N-( l-methyl-2-methoxyethyl)DTP 4 5 9 9N"-( Z-hromoethyl )-DTP 0 2 0 8 N"-isobutyl-DTP 2 8 5 9 N-sec-amyl-DTP 48 9 9 N-(3-pcrlty|)-DTP 4 7 8 9 N scc-hutyl-DTP 4 7 8 9 N".N-diethyl-DTPI 5 7 8 9 N'-methyl-N",N-pcntamethylene- 0 2 9 DTP N-methyl-N"'(3-pentyl)-DTP 3 6 5 9 N'.N'-diethyl-DTP- 3 4 8 9N-sec-butyl-DTP 3 4 9 9 N Z-hydroxyethyl )-N-sec- 0 0 4 9 hutyl-DTP *S0soybeans 0 oats VL velvetleaf Ml millet EXAMPLE XXlll NI-methyl-Z-methoxyethyl )-2,4-dinitro-6-trifluoromethyll,3-phenylenediamine is especially useful for controlling weeds in cornand cotton. For example, an ethanol solution of the compound was appliedto soil at a rate of 0.25 pound per acre and then incorporated by mixingin a greenhouse flat. On the same day, foxtail, wild oats, millet,watergrass, crabgrass, pigweed, velvet leaf and corn were planted in themixed treated soil. The flats were kept in the greenhouse and wateredwhen needed. Fourteen days after treatment the flats were examined andthe plants rated for herbicidal activity, as described in Example XlX.The following results were obtained.

Crahgrass Since a relatively small amount of one or more of the active2,4-dinitro-l ,3-phenylenediamines should be uniformly distributed overthe area to be treated, the compounds preferably are formulated withconventional herbicide carriers, either liquid or solid. Thus, thecompounds can be impregnated on or admixed with a pulverulent solidcarrier such as lime, talc, clay, Bentonite, calcium chloride,vermiculite, calcium carbonate, and the like. Alternatively, thecompounds can be dissolved or suspended in a liquid carrier such aswater, kerosene, alcohols, diesel oil, xylene, benzene, glycols,ketones, and the like. A surfactant preferably is included to aid indispersion, emulsification and coverage. The surfactant can be ionic ornon-ionic, and may be liquid or a solid. The use of the term surfactantherein is intended to include such compounds commonly referred to aswetting agents, dispersing agents and emulsifying agents. Typicalsurfactants include the alkylarylsulfonates, the fatty alcohol sulfates,sodium salt of naphthalenesulfonic acid, alkylaryl polyether alcohols,long chain quaternary ammonium compounds, sodium salts ofpetroleum-derived alkylsulfonic acids, polyoxyethylene-sorbitanmonolaurate, and the like. These dispersing and wetting agents are soldunder numerous trademarks and may either be pure compounds, mixtures ofcompounds of the same general group, or they can be mixtures ofcompounds of different classes. Surfactants can also be included incompositions containing a solid inert carrier,

Concentrated compositions containing the active agent which can besubsequently diluted, as with water, to the desired concentration forapplication to plants and soil are also provided. The advantages of suchconcentrates are that they are prepared by the manufacturer in a formsuch that the user need only mix them with ,a locally available carrier,preferably water, thereby keeping shipping costs to a minimum whileproviding a product which can be used with a minimum of equipment andeffort. Such concentrates may contain from about 5 to about 99 percentby weight of one or more of the active 2,4-dinitro-l,3-phenylenediamineswith a carrier or diluent, which may be a liquid or a solid. Liquidcarriers which are miscible with the active agent or other liquids inwhich the compound may be suspended or dispersed can be used. Asurfactant is also generally included to facilitate such dilution ordispersion in water. However, the surfactant itself may comprise thecarrier in such concentrates.

,The herbicidal composition can include other beneficial adjuvants, such.as humectants, oils and contact agents. Also, other herbicides such asthe sodium borates, sodium chlorate, chlorophenoxyacetic acids,

substituted uraeils and ureas, triazines, benzimidazoles, carbamates,anilides. amides, and haloalkanoic acids, can be included in thefonnulation.

The following examples are presented to illustrate the preparation ofsuitable herbicidal compositions of this invention.

EXAMPLE XXIV percent N'-propargyl-N",N -dimethyl-2,4-dinitro-6-trifluoromethyll ,3-phenylenediamine (powdered) 95 percent Granularclay A granular formulation can be prepared by dry blending the aboveconstituents until uniformly mixed in a rotary mixer. A fine spray ofwater is sprayed onto the mixture, while tumbling, to adhere thecompound to the clay. The material is then air dried while tumbling togive a granular formulation which can be applied to the soil orvegetation by hand or by a mechanical spreader.

EXAMPLE XXV EXAMPLE XXVI 25%N-ethyl-N,N-diethyl-2,4-dinitro-6-trifluoromethyl-l ,3-phenylenediamine5% Aromatic sulfonate-oxide condensate surfactant Xylene The2,4-dinitro-l ,3-phenylenediamine is dissolved in xylene to form aconcentrated solution. The emulsifying agent is then dissolved and aliquid formulation of an emulsifiable concentrate is obtained. Theemulsifiable concentrate can be added to water to dilute it to a desiredconcentration, and then sprayed with conventional equipment onto soil orvegetation.

What is claimed:

1. A compound of the formula:

wherein R R R and R are each selected from hydrogen and lower alkyl, orsaid R R or said R R, taken together represent a polymethylene grouphaving from 2 to 5 carbon atoms or the diethyleneoxy group, with theproviso that at least one of said R and R or R and R represent apolymethylene group having from 2 to 5 carbon atoms or the diethyleneoxygroup.

2. N,N ,N*,N"-di(tetramethylene)-2,4-dinitro-6-trifluoromethyll,3-phenylenediamine 3. N,N ,N,N-di( pentamethylene)-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine 4. N,N-dimethylene-N,N"-di-n-propyl-2,4-dinitroo-trifluoromethyll,B-phenylenediamine.

1. A COMPOUND OF THE FORMULA: 2.N1,N1,N3,N3-di(tetramethylene)-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine 3.N1,N1,N3,N3-di(pentamethylene)-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine 4.N1,N1-dimethylene-N3,N3-di-n-propyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine.